Dyestuff mixtures and process for producing fast gray and black prints



Patented Mar. 12, 1 940 UNITE. STATES] 2,193,751 nYEsTUFF MIXTURES AND PROCESS FOR PRODUCING. FAST GRAY AND BLACK PRINTS Hans Wenk and Fritz Grieshaber, Riehen, Switzerland, assignors to Society of Chemical Industry in Basic, Basel, Switzerland No Drawing. Application-June 21, 1938, Serial No. 215,060.-: In Switzerland June 22, 1937 12 Claims} (ore-2s) p This invention is based on the observation that valuable gray to black prints may be obtained by printing with dyestuff mixtures containing dyestuffs which dye blue to, violet belonging to the benzanthrone series together with indigoid dyestuffs of the general formula group in 2-position and R1 is a benzene radical.

Dyestuffs-of the benzanthrone series which dye rblue to violet are, for instance,those of the dibenzanthrone, the isodibenzanthrone and "the benzanthronepyrazolanthrone series. The indi goid dyestuffs of the above general formula may be obtained, for example, by condensing 1:2- naphththioindoxyl which may be substituted by halogen, for example chlorine or bromine, or its 2-carboxylic acid with a reactive 2'-derivative of isatin which may be substituted. Substituents are for example halogens, such as chlorine and bromine, alkyl groups such as methyl groups and alkoxy groups, for instance methoxy and ethoxy groups.

Especially valuable are those dyestuff mixtures which contain dyestufis of the dibenzanthrone series as well as indigoid dyestuffs of the general formula Hal in which R1 is a halogenated benzene radical; and of these mixtures those give the best results which contain the dyestufi dibenzanthrone and the indigoid dyestufi of the formula obtainable by condensation of 8-ch1oro--'l:2-

" rapid fixing and may be developed by merely naphththioindoxyl with 5-bromisatin-a-chloride. Besides the foregoing dyestuffsthe dyestufi" mixtures may contain the usual orange, brown and yellow dyeing dyestufisfor black toning;

' I instance flavanthrene, pyranthrone, the orange thioindigo and the condensation product from 8 -chioro-l:Z-naphththioindoxylwith the 2- (para-dimethylaininoanil) of 2:1-naphththioindoxyl. 1

The dyestuff mixtures, which may contain the individual dyestuffs in various proportions, may

be made in any desired manner, for example by mixing with dyestufi" powders and converting the mixture into paste or by mixing pastes of the 2 dyestulfs, or the individual dyestuffs may be added to the printing paste. These dyestufi powders or pastes may contain the dyestuffs in nonreduced or reduced condition, for example in the form of leuco-esters. Furthermore, they -may 2 contain various additions suitable for printing, for example a phenol such as crude cresol, a Water-soluble alcohol, for instance glycerine,

ethylene glycol, thiodiglycol, also hydrotropic agents, for instance para-toluenesulfonic acid,

cymene sulfonic acid, urea, sulfite cellulose liquor, benzylanilinesulfonic acid, aliphatic or hydroaromatic acids of high molecular weight or salts thereof which contain at least8 carbon atoms together with organic bases, wetting agentsyemulsifying agents, reduction catalysts, for instance alkali-2:G-anthraquinone-disulfonates, anthraquinone, hydroxyanthraquinone and salts thereof, also heavy metal salts, for instance ferrous sulfate, filling agents, for instance dextrin, starch or sugar, reducing agents, for instance sodium hydrosulfite and finally alkalies, for instance caustic potash, caustic soda, ammonium hydroxide, sodium carbonate, mag- 4 nesium hydroxide or potassium carbonate.

The dye'stuif mixtures may be used in all kinds of textile printing; they are characterized by washing with water; they yield, for example on -5 cellulosic fibers such as cotton, artificial silk from regenerated cellulose, very fast, full, black prints.

The following examples illustrate the invention, the parts being by weight:

Example 1 120 parts of a mixture consisting of 110 parts of wheat starch 170 parts of water, 250 parts of tragacanth mucilage (60 parts in 1000 parts of water) 200 parts of British gum powder 170 parts of potassium carbonate 100 parts of glycerine 1000 parts, which thickening has been boiled for half -an-hour, and 100 parts of hydrosulfite R conc.

then added 50 parts of sodium benzylsulfanilate and 30 parts of water There are 1000 parts The goods, for instance cotton, are printed with the mixture after it has stood for 2 hours and Example 2 18 parts of the dyestuif from 8-chloro-lz2- naphththioindoxyl and 5-b r 0 mi s a ti nchloride,

28 parts of dibenzanthrone paste containing 7.2

parts of dibenzanthrone,

15 parts of fiavanthrene paste containing 2.5

parts of fiavanthrene,

'12 parts of 2:1:2':1-naphththioindigo, containing 1.96 parts of 2:1 :2 1-naphththioindigo,

10 parts of glycerine,

40 parts of sodium benzene sulfonate and a dispersing agent, for instance 2 parts of sulfite cellulose liquor, are ground together in a mill, for instance a cylindrical ball mill, until a homogeneous paste is obtained. This paste is concentrated to 100 parts, for instance on the water bath, and again ground and sifted for homogenising it.

Goods which have been printed with 120 parts of this paste per 1000 parts in the manner described in Example 1 have a fast, full black pattern.

Example 3 45 parts of the dyestuff from 8-chloro-1z2- naphththioindoxyl and 5-bromisatinachloride,

parts of dibenzanthrone paste, containing 19.3 parts of dibenzanthrone,

37.5 parts of fiavanthrene paste, containing 6.25

parts of flavanthrene,

25 parts of 2:1:2:1'-naphththioindigo paste,

containing 4.10 parts of 2:1:2:1'-naphththioindigo, are thoroughly ground with 70 parts of dextrin,

100 parts of sodium cymene sulfonate and about 300 parts of water in a ball mill; the mixture is dried in a suitable manner, for instance in a dust drier, and then finely ground. When used for printing in the manner described in Example 1, this dyestuff preparation yields fast, beautiful black prints.

Example 4 25 parts of the dyestuff from 1:2-naphththioindoxyl and isatin-a-chloride, 30 parts of dibenzanthrone paste, containing 7.6 parts of dibenzanthrone, 15 parts of flavanthrene paste, containing 2.5

parts of flavanthrene, f 15 parts of 2:1:2:1'-naphththioindigo paste,

containing 2.42 parts of 2:1:2':'1-naphththioindigo, 10 parts of glycerine, 20 parts of sodium cymene sulfonate,

5 parts of sodium benzyl sulfanilate and 2 parts of sulfite cellulose liquor are ground together in a cylindrical ball mill. The homogeneous paste thus obtained is concentrated to 100 parts on the water bath and, if desired, again ground.

When applied to goods in the proportion of 120 parts per kilo in the manner described in Example 1, this paste yields deep, fast black shades.

Example 5 120 parts of a mixture obtained by grinding together and subsequently evaporating to 100 parts, v

50 parts of the dyestufl" from 8-bromo-l:2-

naphththioindoxyl and 5-bromisatinchloride in the form of a paste of 40 percent strength (made by grinding the powder with water and 10 per cent of glycerine),

28 parts of dibenzanthrone paste, containing 7.2 parts of dibenzanthrone,

15 parts of flavanthrene paste, containing 2.5

parts of flavanthrene,

12 parts of 2: 1:2 1-naphththioindigo paste,

containing 1.96 parts of 2:1:2:lnaphththioindigo are stirred as described in Example 1, with 700 parts of the same thickening and 100 parts of hydrosulfite R conc. and then parts of urea are mixed therewith.

The goods printed with this product exhibit a beautiful fast black.

When the proportion is parts of the printing paste to 1000 parts of thickening, the print obtained is a fast gray.

Example 6 100 parts of a mixture consisting of .45 parts of the dyestufi' from 8-ch1oro-1z2- naphththioindoxyl and 5-'br0misatinchloride in the form of paste of 50 per cent strength (made by grinding the powder with water and glycerine),

25 parts of dibenzanthrone paste, containing 6A parts of dibenzanthrone,

parts of a bromodibenzpyrenequinone paste, made as described in German Specification No. 566,796 and containing 3 parts of bromodibenzpyrenequinone,

15 parts of 2:1:2':1'-naphththioindigo paste, containing 2.42 parts of 2 1 2 1 naphththioindigo, are 'stirred with parts of a thickening, for instance that described in Example 1,

parts of hydrosulfite R conc.

parts of urea and parts of water thoroughly mixed 1000 parts Using this thickening the mixture produces on cotton black prints having the advantages stated in the introduction to this specification.

Example 7 If in Example 6 there is substituted for the dyestuff of German Specification No. 566,796 15 parts of pyranthrone paste, containing 2.89 parts of pyranthrone, and the printing paste is prepared as follows:

110 parts of the dyestuff paste mixture 700 parts of the thickening prescribed in Example 1 100 parts of hydrosulfite R conc.

80 parts of urea v 10 parts of water 1000 parts there is obtained by following the mode of operation described above a fast black print.

Example 8 If in Example 6 instead of the dyestuff described in German Specification No. 566,796 there are used 15 parts of the dyestufi of German Specification No. 458,598, Example 1 or 2, in the form of a paste, containing 2.5 parts of dichloranthanthrone, and the procedure is otherwise similar to that prescribed in Example 7 of this specification, there are obtained deep, fast black prints.

What we claim is:

1. Process for producing fast gray and black prints, which comprises printing cellulosic fibers with dyestuffs of the benzanthrone series dyeing blue to violet in conjunction with indigoid dyestuffs of the general formula bonyl group in 2-position, and R1 is a benzene radical.

2. Process for producing fast gray to black prints, which comprises printing cellulosic fibers with dibenzanthrone in conjunction with indigoid dyestuffs of the general formula wherein R is a naphthene radical united with the sulfur atom in l-position and with the carbonyl group in 2-position, and R1 is a benzene radical.

3. Process for producing fast gray to black prints, which comprises printing cellulosic fibers With dibenzanthrone in conjunction with indigoid dyestuffs of the general formula H l s 00 wherein R1 is a halogenated benzene radical.

5. Process for producing fast gray to black prints, which comprises printing cellulosic fibers with dibenzanthrone in conjunction with indigoid dyestuffs of the formula a c v 6 \NH 6. Process for producing fast gray to black prints, which comprises printing cellulosic fibers with dibenzanthrone in conjunction with indigoid dyestuffs of the formula '7. Dyestuff mixtures which print cellulosic fibers fast gray to black tints, containing dyestuffs of the benzanthrone series dyeing blue to violet in conjunction with indigoid dyestuffs of the general formula wherein R is a naphthalene radical united with the sulfur atom in l-position and with the carbonyl group in Z-position, and R1 is a benzene radical.

8. Dyestuffv mixtures which print cellulosic fibers fast gray to black tints, containing dibenzanthrone in conjunction with indigoid dyestuffs of the general formula wherein R is a naphthalene radical united with the sulfur atom in l-position and with the carbonyl group in 2-position, and R1 is a benzene radical.

9. Dyestuff mixtures which print cellulosic fibers fast gray to black tints, containing dibenzanthrone in conjunction with indigoid dyestuffs of the general formula wherein R1 is a benzene radical.

10. Dyestuff mixtures which print cellulosic fibers fast gray to black tints, containing dibenzanthrone in conjunction with indigoid dyestuifs of the general formula 12. Dyestuif mixtures which print cellulosic fibers fast gray to black tints, containing dibenzanthrone in conjunction with the indigoid dyestufi of the formula HANS VI'ENK. FRITZ GRIESHABER. 

